Adhesive composition containing {60 -cyanoacrylate as its main ingredient

ABSTRACT

Alpha -CYANOACRYLATE ADHESIVE COMPOSITIONS EACH OF WHICH COMPRISES A Alpha -CYANOACRYLIC ESTER AND A DIACRYLIC ESTER COMPOUND OR DIMETHACRYLIC ESTER COMPOUND WHICH IS ADDED TO THE FORMER ESTER AND ADHESIVES PREPARED FROM SAID COMPOSITION HAVING VERY EXCELLENT HEAT-RESISTANCE.

UnIted States Patent [151 3,692,752 Setsuda et al. 1 Sept. 19, 1972 541 ADHESIVE COMPOSITION [56] Ref r nc s CM CONTAINING a-CYANOACRYLATE AS ITS M AIN INGREDIENT UNITED STATES PATENTS [72] Inventors; Kisuke Setsuda, lchikawa-shi; 2,437,231 3/1948 Mowry ..260/78.5 N Iwakichi Sugiyama, Natashino-shL 2,816,093 12/1957 COOVCI ..260/78.5 N both of Japan 3,247,145 4/ 1966 Masters at a] ..260/78.5 N [73] Assign: Mauumom Seiyaku v Kogyo 3,218,305 11/1965 Kneble ..260/86.1

Kabushiki Kaisha, Menamiyahata,

Primary Examiner-Harry Wong, Jr. lch'kawa Chiba Japan Attorney-Waters, Roditi, Schwartz & Nissen I22] Filed: 7 Oct. 29, I969 v[21] App]. No.: 872,377 57 ABSTRACT a-cyanoacrylate adhesive compositions each Of which Foreign Apphcafinn Pnomy Dam comprises a a-cyanoacrylic ester and a diacrylic ester Oct. 31, 1968 Japan ..43/19425 compound or dimethacrylic ester compound which is added to the former ester and adhesives prepared [52] US. Cl ..260/78.5 N, 117/132, 117/139, from said composition having very excellent heat-re- 260/30.6, 260/31.8, 260/895 5,260/898, sistance.

260/DlG. 43 [51] Int. Cl. ..C08f 15/16 [58] Field of Search ..260/78.5 N, 86.1 R, 86.1 N, 1 Claim, No Drawings BACKGROUND OF THE INVENTION The present invention relates to adhesive compositions having improved heat-resistance, and more particularly to heat-resistant oz-cyanoacrylate adhesive compositions. An a-cyanoacrylate adhesives is generally hardenable at room temperature, is of the one component liquid type, and has a high adhering speed, but has a disadvantage in that it is lacking in impact strength and peeling strength. For eliminating the disadvantage mentioned above, various methods have hitherto been proposed. For example, there are inventions such as U.S. Pat. No. 2,784,127 in which dioctyladipate and other plasticizers are used to improve the adhesive, U.S.' Pat. No. 2,816,093 in which the property of the adhesive is improved by using nitro-cellulose, and US. Pat. No. 2,816,093 in which the property of the adhesive is improved by means of a polymerizable vinyl monomer. In practice, however, extremely strict requirements are necessary, so that in the case of using a-cyanoacrylate adhesive, it is usual to adopt a particular procedure for avoiding peeling load or to moderate any impact applied thereto by means of any impact-moderating material such as rubber. Furthermore, the a-cyanoacrylate adhesive is low in its heatresistance. The adhesives mentioned above are mainly used in precision machines and electric parts, but in said machines and parts there are almost no portions which are exposed to temperatures of about 150 200 C from their operational point of view. However, during their operation, the temperature of some portions are sometimes elevated to about 120 C or more. On the other hand, the strength of the oz-cyanoacrylate adhesives decrease suddenly as soon as the temperature of said adhesives exceeds 100 C. Accordingly,

from a heat-resistance point of view, the commercial acyanoacrylate adhesives cannot be used in practice. In general, when any material is used, it is required that there is a temperature tolerance of about percent above estimated maximum temperature during operation. Accordingly, in order to make the adhesives mentioned above usable for the precision machines and electric parts, a heat-resistance, that is, a strength of at least 50 kglcm preferably 100 kg/cm, at room temperature after heating at 150 C for one hour is considered to be necessary. Under such conditions as mentioned above, the strength of the commercial ozcyanoacrylate adhesives is of the order of 0 20 kg/cm. Since the heat-resistance mentioned above cannot be improved unless the composition itself constituting the adhesive is improved it has been proposed to vary the ester group or to add fl-substituted-ozcyanoacrylate to a-cyanoacrylate in order to improve the adhesive. However, heretofore, there has been no success in obtaining an excellent adhesive.

In general, the a-cyanoacrylate polymer is subject, when it is heated at a certain temperature, to thermal decomposition accompanied by main chain splitting as in the case of methylmethacrylate, but the former polymer is softened at a temperature below said former certain temperature. Accordingly, heat-resistance above said softening temperature cannot be expected. Of course, the temperature range mentioned above is different depending upon polymerization degree, ester composition and the like, but since the strength of the commercial a-cyanoacrylate adhesives disappears at a temperature range from C to C, the softening temperature range of said adhesives may be considered to be the range of 140 150 C. In general, the softening temperature ranges of a high molecular compound can be elevated by introduction of a cross-linking structure into the adhesive composition or by increasing the intermolecular force. As a result of various studies relating to improvement of the heat-resistance of the acyanoacrylate adhesives, the inventors have found that said heat-resistance can be effectively improved by adding diacrylic ester compound or a dimethacrylic ester compound.

SUMMARY OF THE INVENTION Therefore, it is an essential object of the present invention to provide a-cyanoacrylate adhesive compositions having greatly improved heat-resistance.

The above object and other objects of the invention have been attained by adding a diacrylic ester compound or dimethacrylic ester compound to acyanoacrylate adhesive compositions. The characteristic features and the method of producing the adhesive compositions according to the invention will become more apparent and more readily understandable from the following detailed description of the invention.

DETAILED DESCRIPTION OF THE INVENTION As a result of studies relating to improvement of heat-resistance of the a-cyanoacrylate adhesives by using highly polymerizable compounds which are capable of producing a stable solution with acyanoacrylate and are compatible with oz-cyanoacrylate, the inventors have succeeded in improving the heat-resistance of the adhesives by adding at least one kind of the following compounds.

(1) polyether acrylates or polyether methacrylates of the following formula:

CHz=CC0-AOCC=CH2 l 1'. M

(where Y designates hydrogen, methyl, or halogen; A designates (C,,H2n0),,, C,,H2n, wherein n =2, 3, 4 or 5. m is 0 or an integer between 1 and 14). For example, ethylene glycol diacrylate, ethylene glycol dimenthacrylate, diethylene glycol dimethacrylate, diethylene glycol dichloroacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate polyethylene glycol dimethacrylate, etc.

(2) Acrylic or methacrylic esters of his (hydroxyalkyl: phosphonic acid derivatives of the following formu a:

(wherein R designates an aromatic hydrocarbon group such as C li C H (CH an unsaturated hydrocarbon group such as C H -Cl-l=Cl-I, CH =CH or a hydrocarbon group such as (.,H,-,(,H-,. (..H R designates an unsubstituted or acrylate or methacrylate group such as Y has the same meaning as above). For example, bis (acryloxyethyl) phenylphosphate, bis (methacryloxyethyl)B- -phenylvinylphosphonate, bis (methacryloxyacetoxy glyceryl) benzylphosphate, bis (methacryloxychloropropyl) -phenylvinyl phosphonate, bis (dimethacryloxy glyceryl) Bphenylvinyl phosphonate, bis (diacryloxy glyceryl) -B-phenylvinyl phosphonate etc.

(3) Acrylic and methacrylic esters of trishydroxyalkyl cyanuric acid derivatives of the following formula:

(wherein Z designates l=an integer above 2), or

(R and Y have the same meaning as above). For example, tris (acryloxyethyl cyanurate, tris (methacryloxyethyl) cyanurate, tris (methacryloxyacetoxyglyceryl) cyanurate, tris (dimethacryloxyglceryl) cyanurate etc.

(4acrylic esters and methacrylic esters of polyols for example, trimethylol propane trimethacrylate, hexyleneglycol diacrylate. When one or more of the compounds mentioned above (I), (2), (3) and (4) are added in an amount of 0.5 20 percent by weight, preferably 1 percent, based on the a-cyanoacrylate to a-cyanoacrylate adhesives, a significantly improved heat-resistance is imparted to said adhesives. Further, plasticizer and viscosity adjusters such as polymethacrylate may also be used in order to adjust the viscosity of the adhesive composition. However, it is preferable to use the plasticizer in an amount of less than 10 percent because its excessive addition reduces the heat-resistance.

The adhesive composition according to the present invention is stable during a long period of time such as six months or more at room temperature as in the case of conventional a-cyanoacrylate adhesives and can be used in the same condition as that of the latter adhesives. The setting time and adhesive strengths of the present compositions are similar to those of said conventional adhesives and the tensile shear strength of the present composition in the case of mild steel is 210 240 kg/cm at room temperature. However, when the present composition is heated to above C, its strength is considerably higher as compared with the conventional adhesives. For example, at room temperature after heating of the composition for one hour at 150 C, it has a strength of 60 135 kg/cm in the case of mild steel. This means that the present composition has a high heat resistance which is several times that of conventional adhesives.

EXAMPLE 1 6.5 parts of bis (dimethacryloxy glyceryl) -B-phe nylvinyl phosphonate and 0.5 part of polymethylmethacrylate solution are added to 93 parts of ethyl-acyanoacrylate containing 0.001 part of sulfur dioxide and 0.06 part of hydroquinone as stabilizers, and the mixture thus obtained is dissolved homogeneously. A solution having a viscosity of 3 cps (at 26 C) is obtained.

The resulting product has a setting time of 60 sec. in the case of mild steel and of 30 60 sec. in the case of brass. The adhesive strength of said product is 235 kg/cm in the case of mild steel. (This is the tensile shear strength at a tensioning rate of 250 mm/min, measured after curing of the adhesive temperature for 24 hours after adhesion thereof.) Further, the heat-resistance of this product is much higher than that of conventional adhesives as shown in a table set forth hereinafter.

EXAMPLE 2 Similarly as in the case of Example 1, 3 parts of his (dimethacryloxyglyceryl)-B-phenylvinyl phosphate and 5 parts of diethylene glycol dimethacrylate are added to 12 parts of ethyla-cyanoacrylate, whereby a solution having a viscosity of 2cps is obtained. This resulting product has a setting time of 60 120 sec. in the case of mild steel and of 30 60 sec. in the case of brass. The adhesive strength of said product is 248 kg/cm in the case of mild steel, and the heat-resistance of the product is excellent as shown in the later table.

EXAMPLE 3 Similarly as in the case of Example 1, 9 parts of tetraethylene glycol dimethacrylate and one part of polymethyl methacrylate solution are added to 60 parts of ethlyl-a-cyanoacrylate containing 30 parts of methyl -a-cyanoacrylate, and the mixture thus obtained is dissolved homogeneously, whereby a solution having a viscosity of 2cps is obtained.

The resulting product has a setting time of 60 90 sec. in the case of mild steel and of 30 45 sec. in the case of brass. The adhesive strength of the product is 248 kg/cm in the case of mild steel, and the heat-resistance of the product is excellent as shown in the later table.

EXAMPLE 4 Similarly as in the case of Example 1, 7 parts of diethyleneglycol diacrylate and one part of polymethyl methacrylate solutions are added to 92 parts of ethyl a-cyanoacrylate, and the mixture thus obtained is dissolved homogeneously, whereby a solution having a viscosity of 3 cps is obtained.

The resulting product has a setting time of 60 120 sec. in the case of mild steel and of 30 60 sec. in the case of brass.

The adhesive strength of the product is 2 l kg/cm in the case of mild steel, and the heat-resistance of the product is excellent as shown in the later table.

EXAMPLE Similarly as in the case of Example 1, 3 parts of trimethylolpropane trimethacrylate, 4 parts of his (methacryloxychloropropyl)-phenylvinyl phosphonate, and one part of polymethyl methacrylate solution are added to 92 parts of ethyl-a-cyanoacrylate, and the mixture thus obtained is dissolved homogeneously whereby a solution having a viscosity of 3 cps is obtained.

The resulting product has a setting time of 60 120 sec. in the case of mild steel and of 30 60 sec. in the case of brass. The adhesive strength of the product is 220 kg/cm in the case of mild steel, and the heat-resistance of the product is excellent as shown in the later table.

EXAMPLE 6 Similarly as in the case of the example 1, 6 parts of the methacrylic ester of tris (methacryloxyethyl) cyanurate and one part of polymethylmethacrylate, and the mixture thus obtained is dissolved homogeneously, whereby a solution having a viscosity of 4 cps is obtained.

The resulting product has a setting time of 60- 120 sec. in the case of mild steel and of 30 60 sec. in the case of brass.

The adhesive strength of the product is 218 kg/cm in the case of mild steel, and the heat-resistance of the product is excellent as shown in the later table.

EXAMPLE 7 Similarly as in the case of the example I, 5 parts of tris (methacryloxyethyl) cyanurate and 2.5 parts of bis (dimethacryloxyglyceryl)-B-phenylvinyl phosphonate are added to 92.5 parts of ethyl-a-cyano-acrylate, and the mixture thus obtained is dissolved homogeneously, whereby a solution having a visosity of 3 cps is obtained. The resulting product has a setting time of 60 90 sec. in the case of mild steel and of 30 45 sec. in the case of brass.

The adhesive strength of the product is 230 kg/cm in the case of mild steel, and the heat-resistance of the product is excellent as shown in the later table.

The strength (heat resistance) of each sample bonded with each of the products obtained by the above Examples 1 7, inclusive, after heat treatment is shown in the following table.

As is apparent from the following table, the heat resistant adhesives of the present invention are excellent in their strength after heat treatment as compared with those of commercial products of similar kind.

MEASURING CONDITION Mild steel pieces 100 X X 20 mm) are lapped and bonded with adhesive according to the present invention and then subjected to curing for 24 hours at room temperature. This cured product was heated at 150 C for 60 minutes in a heating furnace and then cooled to room temperature, and tensile shear strengths thereof were measured.

Specimen Strength after heat treatment A part 0-5 kg/cm was stripped off during heat treatment Commercial Product A Commercial Product 8 Example I ov-bu Where:

Eastman 910 Visca 18M COMPOSITION Eastman 910 Methyla Cyanoacrylate or Ethyl Methyl a Cyanoacrylate added with the following plasticizer below 10 percent. Dibutyl sebacate Diethyl adipate Triphenyl phosphate Visca 18M ll 0 Y where R, is an aliphatic or aromatic hydrocarbon group; R is an unsubstituted alkylene group having two to eight carbon atoms, or a substituted alkylene group having two to eight carbon atoms and as substituents,

halogen, fatty acid carboxylate, acrylate or methacrylate group; and Y is hydrogen, methyl or halogen; and

2. an ester having the general formula where Z is wherein Z is an integer having a value of at least 2, or

wherein R, and Y have the same meanings as given under(l). 

2. an ester having the general formula 